JPH04169588A - 1,1,3,3-tetramethyl-1-vinyl-3-(2-phenylethenyl)disiloxane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides novel organosilicon compounds 1, 1.3.3-tetramethyl-1-vinyl-3 useful as crosslinking agents and modifiers for organic polymers. -(2-phenylethynyl)disiloxane.

[Problems to be solved by conventional techniques and inventions] Conventionally,
To be able to vulcanize organic polymers such as polyacrylates, polystyrene, and polyethylene-propylene copolymers with peroxides, monomers such as butadiene and ethylidene norbornene with two vinyl groups are copolymerized as crosslinking points. It is well known that there are.

However, when copolymerizing a crosslinking monomer with an organic polymer such as the one described above, instead of butadiene, ethylidenenorbornene, etc., vinyl groups that are copolymerized with the organic polymer and vulcanized side chains that are not copolymerized with the organic polymer are used. A monomer having two types of vinyl groups that differ in their reactivity with vinyl groups that serve as crosslinking points is sometimes desired.

In addition, as such 7-mers, methacryloxy-containing vinyl siloxane (Japanese Unexamined Patent Publication No. 14787/1987) and P
-Silicon compounds with vinylphenyl groups (JP-A-62-
No. 215,608) has been proposed, but a compound in which a phenylethynyl group and a vinylsilyl group are bonded via a siloxane bond has not been known so far.

[Means and effects for solving the problem] The present inventors,
In view of the above-mentioned demands, as a result of intensive studies, we found that, for example, styrene is reacted with an organohydrodiene silane or siloxane to obtain an intermediate having a phenylethynylsilyl group, and this is reacted with a silane or siloxane having a vinylsilyl group. By this, a novel organosilicon compound having a phenylethynyl group and a vinylsilyl group in one molecule, that is, 1,1,3.3-tetramethyl-1-vinyl-3-(2 - Phenylethynyl) disiloxane can be obtained, and this organosilicon compound has two types of vinyl groups with different reactivity, phenylethynyl group and vinylsilyl group, and when copolymerized with an organic polymer, that the vinylsilyl group is not copolymerized with the organic polymer, and only the phenylethynyl group is copolymerized;
This made it possible to introduce a vinylsilyl group into an organic polymer, and it was discovered that an organic polymer copolymerized with the above-mentioned organosilicon compound can be vulcanized using the vinylsilyl group as a crosslinking point, and the present invention This is what we have come to do.

The present invention will be explained in more detail below.

The novel organosilicon compound according to the present invention is represented by the above formula (1)! , 1,3.3-tetramethyl-1-vinyl-
3-(2-Phenylethynyl)disiloxane is a colorless and transparent liquid with a boiling point of 85-87°C/2mmHg, and a refractive index n25°C of 1.4770 at 25°C.

This new compound consists of styrene and dimethylchlorosilane,
By reacting an organohydrodiene silane or siloxane such as pentamethyldisiloxane in the presence of a catalyst,
An intermediate having a phenylethynylsilyl group is obtained, and a silane or siloxane having a vinylsilyl group is obtained, such as vinyldimethylchlorosilane, 1,3-divinyl-1,1,
It can be synthesized by reacting with 3,3-tetramethyldisiloxane. In addition, as the above-mentioned catalyst, Ru catalyst (Seki et al., J, O
rg, Chem, 1986°51, 3890)
, Rh catalyst (Onopchenko et al.
.

J, Org, Chem, 1983.48.51
01), Os catalyst (S p e i e r e t
a 1 , A d v , Or ga no
m et a IChem, 1979. 1
7.407), etc., but Ru catalysts are preferably used from the viewpoint of yield.

Alternatively, a method may be employed in which an intermediate having a phenylethynylsilyl group is synthesized by reacting phenylacetylene and organohydrodienesilane in the presence of chloroplatinic acid.

The novel compound of the present invention is effective as a crosslinking agent or a modifier for organic polymers, such as polyacrylate, polymethacrylate, polystyrene, polyethylene-propylene copolymer, etc. -Butyl hydroperoxide/F
eC1□/4-15°C using ascorbic acid etc. as a catalyst
In this case, the new compound contains a phenylethynyl group, which is a vinyl group activated by a phenyl group, and a vinylsilyl group, which has low reactivity, in one molecule. Therefore, vinylsilyl groups can be introduced into organic polymers such as those mentioned above, and these can be used as crosslinking points for vulcanization. Furthermore, when an organic polymer copolymerized with this new organic compound is vulcanized, it has high heat resistance because the crosslinked structure has a siloxane skeleton that has high thermal stability.

〔Effect of the invention〕

The novel compound according to the present invention has two types of vinyl groups with different reactivities, a phenylethynyl group and a vinylsilyl group, bonded via a siloxane bond, so it is useful as a crosslinking agent and a modifier for various organic polymers. be.

Hereinafter, the present invention will be specifically explained with reference to Examples.

〔Example〕

208 g (2 mol) of styrene and 148 g (1 mol) of pentamethyldisiloxane are charged into a three-bottle flask equipped with a reflux condenser, a thermometer, and a stirrer, and after degassing, nitrogen substitution is repeated three times. Rus (CO
) 120, 18 g (0.05% by weight),
Heat and stir at 80°C. After 5 hours, analysis by gas chromatography revealed that 1, represented by the following formula (2),
93% 1,3,3.3-pentamethyl-1-(2-phenylethenyl)disiloxane, 96% ethylbenzene
% yield.

After the reaction mixture was transferred to a rotary evaporator, a small amount of raw materials and ethylbenzene were removed, and then transferred to a still and vacuum distilled at 2 mm Hg to obtain a boiling point of 82-83
C. fractions were collected to obtain 228 g (yield 91%) of the compound of formula (2) above. The properties of the compound of formula (2) are as follows.

Jin 11th grade n Boiling point 282-83°C/2 mm Hg 25°C.

nD, 1.4881 NMR (CDCl2.δppm) near, 31-7.52 (m, CeHs, 5H) 7.0
3, 6.98, 6.51, 6.46 (dd, C=C
-H.

0.18 (s, Si (CH=)s, 9H)IR(
cm”): See Figure 2 3025.2991, 2958.2900 (Si-
CH3) 1606.1575, 1495, 144.8
(CAL) 1254 (CH3) 1055 (SiO5i) Next, 228 g (0.91 mol) of the above compound (2)
, KOHQ, 056 g (1 mmol) were placed in the same three-bottle flask as above and stirred at 150° C. for 1 hour under a nitrogen stream. Next, an ester adapter was installed between the reflux condenser and the generated hexamethyldisiloxane was removed while purging with nitrogen. After removing the ester condenser, divinyltetramethyldisiloxane 260
g (1,39 mol) and stirred at 150°C for 5 hours. After cooling, it was neutralized by adding a small amount of N)L and CI, and then distilled under reduced pressure to a boiling point of 85-87°C/2 mm Hg.
172g (0,655 mol) of the fraction was collected and the above (
The target compound 1,1,3.3-tetramethyl-1-vinyl-3-(2-phenylethynyl)disiloxane represented by the formula 1) was obtained in a yield of 72%. Its properties are as follows.

Boiling point of person 1 = 85-876C/2 mm Hgn25℃:
1.4770 NMR (CDC, δppm) Near, 26-7.49 (m, C, H,, 5H) 6.4
3,6.49,6.96,7.00 (dd, C=C
-H.

2H) 5.75-6.24 (m, 5i-CH=CHL, 3
H) 0.29 (s, Si (CH3)2CH=CH,
, 6H) IR (cm”): See Figure 1 3052, 3026, 2960, 2902 (S
i-CH3) 1597.1575, 1495.14
48 (αH5)1256 (CH3) 1054 (SiO5i) [Reference example] In the same manner as in Example 1, 2-
A crude product of phenylethynyldimethylchlorosilane was obtained, which was concentrated using a rotary evaporator and 2
95 g of concentrate was obtained. 120 g (1 mol) of vinyldimethylchlorosilane are added to this and the mixture is added dropwise to 2 liters of water under vigorous stirring. After the dropwise addition, the mixture was stirred at room temperature for 2 hours, extracted with toluene, washed with water until neutral, and dried with M g SO 4 . After concentrating this toluene solution using a rotary evaporator, 2 m
Distilled under reduced pressure at m Hg to obtain the formula (1
) 144 g of the compound shown (0.55 mol, yield 5
5%) and 25 g (0.07 mol) of a compound represented by the following formula (3) were obtained.

In addition, the properties of the compound of formula (3) are as follows.

Boiling point: 118°C/2 mm Hgn25°C: 1
．． 5444 NMR (CDCL, δppm) Near, 317.50 (rn, CsL, 10H) 6.49
,6.54,7.0,7.06 (dd, C=CH,4
H) IR (am-'): See Figure 3 3024.2991, 2958.2900 (Si-C
H3) 1606.1574, 1495.1448 (C
6H5) 1255 (cHj) 1049 (SiO5i)

[Brief explanation of drawings]

Figure 1 shows 1,1,3,3-tetramethyl-1-vinyl-
Figure 2 shows the infrared absorption spectrum of 3-(2-phenylethynyl)disiloxane. Figure 3 shows the infrared absorption spectrum of 1,1.3,3.3-pentamethyl-1-(2-phenylethynyl)disiloxane. It is an infrared absorption spectrum of 1,1,3.3-tetramethyl-1,3-bis(2-phenylethynyl)disiloxane. Applicant Shin-Etsu Chemical Co., Ltd. Agent Patent Attorney Takashi Kojima

Claims (1)

[Claims] 1. 1,1,3,3-tetramethyl-1-vinyl-3-( represented by the following formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.▼...(1) 2-phenylethenyl)disiloxane.